Diazotype dyeing and printing of web or sheet material



Patented Nov. 4, 1952 UNITED "STATES ,v OFFICE DIAZ'OTYPEDYEING PnINTmG'oF WEB on SHEET "MATERIAL? J Leonard E. Ravich,. New-York,- .NrYr

No'Drawing', Application March 11, 1948,

Serial No. 14,400

This invention relates to continuouszdyelng and-printing of web or sheet materials 'and more 1 particularly to methods forproducingstabledye images or patterns on textile fabrics, papergiand other web or sheet materials.

It 'tis. the' principal object of the present vin-- ventionlto provide improved processes of 'ap-- .p'ly1ng;rby"coating .or'impregnating, in the'iform of fimagessor fields; one or1more: colors of "azo dyes.

'It isviafurther object of .theapresent:invention to provide improved. processes of applying, by-

impregnating ,or coating, oneor more .colors in a continuous application.

I It is .a further object of thepresentinvention to provide improved processes of applying. by impregnating or coating, one or more colors in which standard dyeing materials soluble in or capableofsuspension in liquid vehicles other than water, are employed so that restriction to the use of water soluble coupling agents is unnecessary.

the dye intermediate to form insoluble colorcompounds on the web or sheet material.

In order to illustrate the invention the following specific examplesare given, but it'is'to be understood that the invention isnotlimited to the particular' products nor materials 'mentioned therein nor to the specific order of steps as set forth; It is intended however that the sheet or web material be successively and'con tinuously treated to obtain the desired results;

EXAMPLE 1 A: photoesensitive dye. intermediate aqueous solution may :be. pprepared eonsisting *ot the following; i Y

Formulazliorilz Zinc chloridedouble salt of2' -metl 1fyl diw thenyl-4z4 diazo-sodium sulphite' 7 gramsem Boric'acid Watem ;.cubicr:centimetersz 1000 21. A coupling compound in ert-solution of isopropy alcohol (which is not a solvent for the dye intermediate oi Formula No'; 1) "may be prepared consisting' of the following;

Formula N0. 2

Isopropyl alcohol -cubic"centimeters 100 'B'eta-naphthol "grams; 5

The sheet'orweb tobe' dyed 'or' printed is coated or impregnated with a photo-sensitive dye intermediate inaliquid form and in accordance with; the formula given in Formula No. l. The web iisthen driem or permitted :to dry, under alkaline free conditions, and the sheet or 7 web is next impregnated or coated with a solui following may be e'lfipldydi tionpf f'a coupling compound in a solvent or liquid vehicle; such as that" of 'Formula No. 2, in which the dye intermediate "is not soluble, and the sheet 'or""w'eb'is alsodri'ed, or permitted to dry; The sheet or"w'e bls" then exposed to a strong" actinic" light" source j directed through a photo "plate-"or similar lightscreen and on which there is reproducedthe-pattern or "design tube applied to the sheet or web: The sheet 'or web,

7 immediately thereafter; is passed into or through a chamb'ercontainingwater vapor-and an alkaline-medium; such as ammonium hydroxide; or through an alkaline solution, until the color coupling takes place and an imageis produced on the" sheet or web. The imagethuspbtaineu is an exactreproduction' or "the photo plate or its equivalent;

Ifdesir'ed the diazo; such as that of Formula nd. 1; may'be'applied to'thesheet or web and after drying," the sheet "or*web'm'ay be exposed as before-for printing! The coupling compound, as in' Formula' No. may "then' be applied. If desired; also an" alkaline component maybe added to or applied with the coupling compound and 'thematerial thus f-treated" subjected" to water vapor-orsteamfondevelopmentof the color. If thisdatter procedurvb'e followed the separate treatment in the chamber in an alkaline environment will not be necessary.

As illustrative of' other 'sui tablematerials the A photo-sensitive eveintermediate solution is prepared cons'istin'g of the "following:

F ii'mlllaiNo. 3Q

Copper? sulpliatesdoubles salt'zoi dfazoti'zed;

A coupling compound in another solvent or vehicle in which the dye intermediate is not soluble is also prepared consisting of the following:

Formula No. 4 2-hydroxy-3-naphtholic acid grams '5 Ethyl alcohol cubic centimeters 100 The sheet or web material is treated as before, being impregnated first with the material of Formula No. 3, and, when dry, with the material of Formula No. 4, exposed under a photo plate and passed into an alkaline atmosphere or solution.

As illustrative of other suitable materials, the

following may be employed; I

EXAMPLE 3 A photo-sensitive dye intermediate solution is prepared consisting of the following:

' FormuZa'No; 5

Zinc chloride double salt ofortho-amino-.

azo-toluene grams, 5 1% carboxy methyl cellulose I cubic centimeters 500 Lactic acid, do 10 Aluminum sulphate grams 10 A coupling compound is also prepared consisting of the following:

"FormuZa No. 6

Beta-naphthol gra'ms 10 Lactic acid cubic centimeters 1000 Isopropyl alcohol do 10 warm air blast. The color may then be developed by subjecting the sheet orv web toammonia vapor,

as before. V I

Coupling, as hereinbefore referred to, can be effected at room temperatures, orif desired elevated temperatures may be employed for increasing the speed of operation, enhancing the penetration into the fibres of the web or sheet material, and enhancing the color fastness. If it is desired to employ elevated temperatures the coated material, during and immediately after coupling, is subjected to live steam or boiling water.

It is not necessary to employ stabilizers, not only because the process is continuous, but also because the printing takes place too rapidly to permit of decompositionof constituents which might be unstable.

The diazo components utilized as dye intermediates in the practice of the present invention must be insoluble in the solvent of the coupling agent and may be any of those generally employed in the diazotype are and having this characteristic, and including diazotized members of strongly basic monoamine groups, such as aniline, phenols, amines, toluidines, xyledines,

aminophenols, pyrazolones, carbazoles, sulfones,

naphthols, acetoacetic acid esters, acetanilides, 'monochloroderivatives of the benzenoideaminegroup where the chlorine atom is meta to the amino group, diaminesi of the benzldine series,

and alpha and beta-naphthylamine. Other dye intermediates include the sulphonamide and the diphenylamine groups.

The diazos may be utilized as such, or in the form of their stabilized double salts, such as with zinc chloride, cadmium chloride, tin chloride or the like, as the fiuoroborates, as the alkyl or aryl sulfonates, such as methyl, ethyl, propyl, phenyl and the like sulfonates, or as the sulfates.

Any suitable diazo coupler which is insoluble in the diazo solvent may be used, the coupling agent being a phenolic or naphthoic coupler, or active methylene compounds, such as betanaphthol, 2 hydroxy-3 naphthoic acid anilide, diacetoacetictolidide, p-hydroxynaphthoic acidp-nitroanilide, beta-hydroxynapthoic acid-betanaphthalide, 1:8 aming-naphthol-2z4 disulphonic acid, 4-hydroxy-6 methyl-2 (l) pyridone, and

'phloroglucides.

A wide range of colors is available for producing the preferred color or color pattern on the sheet or web.

As examples of color coupling in accordance with the present invention and the colors obtained therewith, the following have been found suitable, it being noted that the liquid medium employed as a solvent for the dye intermediate is not a solvent of the coupling compound and the liquid medium employed with the coupling compound is not a solvent of the dye intermediate:

a. naphthyl- Beta-naphthol plus diazotised dianisidinezBlue 7 Beta-naphthol plus diazotised metanitraniline:

5 p ual adjuncts, such metal salts for intensifica- Orange Beta-naphthol plus diazotised nitro-o-toluidine:

Darker orange Beta-naphthol plus diazotised p-nitroorthotolu- 4-hydroXy-6 methyl-2(1) pyridone plus diazotized p-ethylaminoanilinezviolet l :8 amino-naphthol-2z4 disulphonic acid plus diazotized p-aminodiphenylaminezviolet Phloroglucide plus diazotized diethylaminobenzenezViolet In addition to the diazo compound and coupling agents, the sensitizing solution may. contain the .wagents: such: as: ;.thiourea,: thiosinamine; naphtha- :vlene ztrisulfonic; acid, and: the like; :may contain acids for retarding precoupling, :such asJcitric acid; boric acid, tartaric acid, ;or.;mixtures thereof, land the ilike; may contain rhydroscopic agents, suchzasiethylene gIycOL-glycerine, fdextrinandz the :like may contain: solvents such: as isopropyl-:al- .1cohol, (3ellosolve,iand the. like ;-:may :contain ewettrting agentspsuch:as saponinasulfonated :alcohols can'd t'he like, fatty acids suchaa asulphonated rcastor oil? and ithe alike; and rmay :also contain i-thi'ckening agents, such as carboxy; methyl: celi lulose;starch -and the' 'like.

With the materialsheretofore :referred :.to, a isin'gle'colorselectedfrom -.a.= wide range of colors may-be applied upon asheet orweb. Immediately followingithe application of one color, if i desired, the process maybe repeated one or more-times to apply' one or more 'diiferent colors successivelyfto the same sheet orweb and without objectionable effects on the'previouslyapplied C0101"I'CO10 1S.*

Inaccordance with the present invention; also, twoor more-colors maybe simultaneouslyprinted on-thesheet or'web in a continuousprocess.

"If'it -is desired toapply more than one-color substantially the-same procedureasheretofore -re'ferred*tomay' be employed; The "material is however coated'or impregnated with a solution of a dye intermediate which is not light sensitive or is weakly light sensitive. After thefsheet or "web has been dried, or-permitted to dry, under i alkalinefree conditions, a solution of a light -sensitive dyein a' fluid medium other than that used in the-'first application is-applied to the sheet or web.

The first-dye intermediate employed "is one -which-isnotsoluble in the "solution of the material employed for the second coating or impregnation and the light sensitive dye intermediate employed; in the second coating on impregnating solution is not'solublein thesolution of thefirst-dye intermediate.

The, sheet or web, after the application of th second coatingor impregnating solution, is dried,

or permitted to. dry, under alkaline free conditions, and a solution of the coupling compound is applied. The liquid used in the solutionof the coupling compound i not miscible-with those used with the first dye intermediateand the light sensitive dye intermediate. I

The sheet or web, asthus, prepared, is eggposed under avphoto plate, asbefore, to an actiniclight source, and immediately; passed througha cham- ,.ber containing water vapor andan alkalinegpe- 'dium such as ammonium hydroxide, or'through an alkalinetsolution until 'color coupling takes place and an imageof one color is produced against a background of another colorzon the web :or, sheet. -material.

Asa particular illustration of suitable materials to be employed for this purpose, the following may be employed.

EXAMPLE 4 A solution of a dye intermediate which is not light; sensitive or which is weakly light sensitive is prepared and may consist of the following:

Forniula No. 7-YeZZow background color, (weakly light sensitive dye intermediate) rmsolutionwfza:li husensitire-.dreiintermedia marsh .zza soprepared con aining theeiollowin r "Formula No. '8"'i3l ue, "light-sensitive, ;jdye

intermediate Diazotizedidianisole sodiumrsulphite grams :10 aQopper: sulphate do' 5 Bol-icwacid. q :dQ..,. .10 4.1.0 -Wa cr a, M. cubimcenti-meters. 1008 -A-coupling solution is al so prepared preferably containing the following:

EormuZai-NQ. .9-.-cqupling solution Beta-maphth'01 ;.grams 5 Stearic acid do 5 Benzene -cubic centimeter-""1 00 .The m erials .-.a thus prepared :a ap lie was indicated ,above, and an ime e ofprierpolor will? be producedagainsta background of; another color on the sheet or web.

r'Ifhe; ordenof applicationof :the various materials izmaysalso bevaried .as indicated, in, connection with the precedingr.exam-ple,,,and with. ,adjunct, materials included, -a-nd with coupling ac companied by.-,=elevated temperature conditions.

If. desired,;also,- ,aiter completion; he process may the repeated one or more times to;- apply-,one. or moredifierenti andvajdditional- ,colors' tothe-sheet :orweb.

I claimt fThemethod .of applying:color to -.-web;or 1 sheet material which comprisesrfapplyingz to the -material -ra photosensitive diazo compound in; a

plingaagent ,in a: liquid vehicle in which, the diazo compound is insoluble, and which coupling agent :is-insolublein said liquidmedium,sunder the con- 40 v:ditions of athe'aprocess, -;exposing :the material-:to

which/i. the :coupling :agent and diazo :scompound have been applied :to a flight "source directed through;av.color-;-pattern determining screen for :determining;the -pattern ofcoloron the material, and exposing thevmaterial. to an alkaline renvvironment.

22. .-;'I he= :method applying color to -.web or sheet ;;mater-ial' :which. comprises in a! continuous proc- ":essaapplyingto zthei drymaterial a photosensitive diazo compound in a liquidsmedium; applying to (the dry material a coupling agent in :a liquid wvehicleoinrwhich thegdiazo compound is insoluble yandizwhich.couplingsagentis-insoluble in said liq- --uid-,. medium exposing the material. to which-the -couplingwagent and. diazo. compound have been iappliedvtora lightsource,directed-through a color epattern determining :screen for determining the pattern of color on the material an'd' then exposingthe material to a-n alkaline environment.

.'iThermethodr-as'set forth inclaim l in which Zithe tmaterial duringacoupling issu-bjecte'd to an elevated-ternperature.

The rmethod of applying a-pluralityofcolors to web or-: "sheet" material Which-comprises applying to the material a diazo compound which is weakly or non light sensitive in a liquid carrier, applying to the material a photosensitive diazo compound which is insoluble in the liquid carrier in a liquid medium in which said first diazo compound is insoluble, applying to the material a coupling agent insoluble in said liquid carrier and said liquid medium in a liquid vehicle in which said diazo compounds are insoluble, then exposing the material to which the diazo compounds and coupling agent have been applied to a light source directed through a color pattern determining screen for determining the pattern of the color and then exposing the material to an alkaline environment.

5. The methodof applying a plurality of colors to web or sheet material which comprises in a continuous process, applying to the material a diazo compound which is weakly or non light sensitive in a liquid carrier, then applying to the material a photosensitive diazo compound which is insoluble in the liquid carrier in a liquid medium in which said first diazo compound is insoluble, then applying to the material a coupling agent insoluble in said liquid carrier and said liquid medium in a liquid vehicle in which said diazo compounds are insoluble, then exposing the material to which the diazo compounds and coupling agent have been applied to a light source directed through a color pattern determining screen for determining the pattern of the color and then exposing the material to an alkaline environment.

6. The method as set forth in claim 4 in which the material during coupling is subjected to an elevated steam temperature.

7. The method of applying a plurality of colors to web or sheet material which comprises in a continuous process, applying to the material a photosensitive diazo compound in a liquid medium, applying to the material a coupling agent insoluble in said liquid medium in a liquid vehicle in which said diazo compound is insoluble, exposing the material to which the diazo compound and coupling agent have been applied to a light source directed through a color pattern determining screen for determining the pattern of the color, exposing the material to an alkaline environment, and repeating the aforesaid steps with a diazo compound and coupling agent which provide a difierent color, said last diazo and coupling agent each being insoluble in the liquid medium or vehicle of the other.

8. The method of applying color to web or sheet material which comprises applying to the material a photosensitive diazo compound in a liquid medium, applying to the material a coupling agent in a liquid vehicle in which the diazo compound is insoluble and which coupling agent is insoluble in said liquid medium, and developing and fixing the color.

9. The method of applying colors to web or sheet material which comprises in a continuous process, applying to the material a photosensitive diazo compound in a liquid medium, applying to the material a coupling agent insoluble in said liquid medium in a liquid vehicle in which said diazo compound is insoluble, and developing and fixing the colors. 7

10. The method of applying a plurality of colors to web or sheet material which comprises in a continuous process, applying to the material a photosensitive diazo compound in a liquid medium, applying to the material a coupling agent insoluble in said liquid medium in a liquid vehicle i in which said diazo compound is insoluble, forming an image with a light source and fixing the color, and repeating aforesaid steps with a diazo compound and coupling agent which provide a different color, said last diazo and coupling agent each being insoluble in the liquid medium or vehicle of the other.

11. The method of applying color to web or sheet material which comprises applying to the material a photosensitive diazo compound in a liquid medium, exposing the material to which the diazo compound has been applied to a light source directed through a color pattern determining screen for determining the pattern of color on the material, applying to the material va coupling agent in a liquid in which the diazo compound is insoluble, and developing the color.

12. The method of applying a plurality of colors to web or sheet material which comprises apply ing to the material a diazo compound which is weakly or non light sensitive in a liquid carrier, applying to the material a photosensitive diazo compound which is insoluble in the liquid carrier in a liquid medium in which said first diazo compound is insoluble, then exposing the material to which the diazo compounds have been applied to a light source directed through a color pattern determining screen for determining the pattern of the color, applying to the material a coupling agent insoluble in said liquid carrier and said liquid medium in a liquid vehicle in which said diazo compounds are insoluble, and developing the color.

13. The method of applying color to web or sheet material which comprises applying to the material a photosensitive diazo compound in a liquid medium, applying to the material a coupling agent in a liquid vehicle in which the diazo compound is insoluble, and which coupling agent is insoluble in said liquid medium, exposing the so treated material to an alkaline environment,

and, prior to the alkaline exposure and subsequent to the application of the diazo compound,

, exposing the material to a light source directed through a color pattern determining screen for determining the pattern of color on the material.

LEONARD E. RAVICH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. THE METHOD OF APPLYING COLOR WEB OR SHEET MATERIAL WHICH COMPRSES APPLYING TO THE MATERIAL A PHOTOSENSITIVE DIAZO COMPOUND IN A LIQUID MEDIUM, APPLING VEHICLE IN WHICH THE DIAZO PLING AGENT IN A LIQUID VEHICLE IN WHICH THE DIAZO COMPOUND IS INSOLUBLE, AND WHICH COUPLING AGENT IS INSOLUBLE IN SAID LIQID MEDIUM, UNDER THE CONDITIONS OF PROCESS, EXPOSING THE MATERIAL TO WHICH THE COUPLING AGENT AND DIAZO COMPOUND HAVE BEEN APPLIED TO A LIGHT SOURCE DIRECTED THROGH A COLOR PATTERN DETERMING SCREEN FOR DETERMINING THE PATTERN OF COLOR ON THE MATERIAL AND EXPOSING THE MATERIAL TO AN AL KALINE ENVIRONMENT. 